Catalytic process



Jan. 4, 1944. J. A. GUYER CATALYTIC PROCESS Filed Jan. 5, 1942 PatentedJan. 4, 1944 OFFICE cn'rALY'rrc rnocass Jesse A. Guyer, Bartlesville,Okla., assignor io Phillips Petroleum Company, a 4corporation ofDelaware Applicatlonlanuary 5, 1942, Serial No. 11.25.685v

This invention relates to an improved process for conducting catalyticreactions and in pariS-Pelodically regenerated by the use of oxygen-@.Qlvlihflg gases.

i features oftfiinvention are applicable .to any catalytic reaction inwhich 'a stream orstreams or reactants to be catalytically treated orconverted are heated and in which the catalytic treatment or conversionof thereactants is acticular to catalytic processes in which thecatalyst complished in one reaction vessel while simultacorporate intothe plant design and equipment a suillcient number ofcatalyst-containing cham`- bers, usually three or more, so that aregular cycle of converting and reactivatingoperations is possible. Sucha cycle ordinarily includes a treating period during which a unit volumeof the catalyst is employed 'in the conversion and a reactivating periodduring which the said unit volume oi catalyst is subjected in situ tocontrolled combustion conditions by the passage of an oxygen-containinggas at or above the ignition temperature of the carbonaceous deposits.

Reactivation of solid granular catalyst masses by combustion 'requirescareful cotrol of the rate oi burning to prevent deterioration of thephysical and catalytic properties thereof, and to prevent damage toequipment, by excessive temperatures. Heat transfer within the catalystmass is poor vdue to' the non-conducting nature of the particles, andtemperature control during combustion is usually attempted by theregulation of the oxygen content of the combustion atmosphere passedthrough the catalyst mass to thereby limit the exothermic heat generatedper volume o! gas. In this manner the combustion atmosphere may serve asboth the temperature control mechanism and the principal heat transfermedium. During the period of reactivation it is ,often desirable toincrease the oxygen concentration of the combustion atmosphere as thecarbon content of the catalyst decreases, tomaindried, re-heated andthelike to 2 calms.' '(01. 19e-2a) tain a reasonably constant temperatureand vto speed the reactivation operation. A

However, the operatingdilculties insuch a procedure are centered in theregulation of the oxygen content of the combustion atmosphere. Noordinarily available gases have an oxygen content in the range requiredduring the initial stages of' reactivation which should -be in range ofsay 0.5 to 3 volume percent.

- Various methods have been proposed for producing and maintainingylarge volumes of gases of very greatly reduced oxygen content. It hasbeen proposed, for example, to recycle the combustion atmospheresubsequenty to passage through the catalyst'undergoing reactivation as asource of substantially oxygen-free gas. Such recycle gas may then belblended with oxygencontaining gas in producing a combustion atmosphereof controlled oxygen content.` This procedure is complicated by thevfactthat this recycle gas may have a substantial and iluctuating oxygencontent atvarious intervals throughout the combustion period. This maybe due to the fact that in the reactivation of catalysts disposed inmultiple-tube reactors, the combustion may proceed unevenLy due tounequal pressure drops in the various tubes. y Similarly, in catalystvessels of relatively largehcross-sectio'nal area uneven combustion mayresult from uneven carbon deposition. The necessary continualre-proportioning of the gas streams being` mixed introduces expensiveand troublesome operating control. Further, prior to recycling, theemuent combustion gas from the catalyst being reactivated is ordinarilychemically treated and/or scrubbed.

remove components deleterious'to the'catalyst or to the reactivatingequipment, which involves additional complication and expense.

It has also been proposed to supply the required substantiallyoxygen-tree lgas in the form of steam. Such proposals are not feasiblein many cases due to the high cost of providing the large amounts ofsteam required as well as to the frequent deleterious eiects of highconcentrations of steam on the catalyst. Inthe latter instance,

lcontrol of the steam content as well as or the oxygen content of thecombustion atmosphere may lead to the multiplication of control problemsand to the use oi expensive cooling and re-heating procedures to removeexcess steam `by condensation and to re-heat the combustion atmosphereto ignition temperatures.

It is an object oi thisinventlon to provide an the' I heating'fafurnacebylx'imiifv n r r a manner as to `use up substantially all theoxygen heataexchangeftherein, (5),. .p y,

actants over .-a catalystioraccomplishin V1siredconversion..Variousheatftran ,-f mentszareaincludedtn give a comple elygcatalyticprocessg, r

Inlorder to poi f vention is improvedprocessior .cariymi utcatalyticreactions. g L

f Another object, oi'` this invention is` to .provide y a moreeconomical processfor'carryingzout cata,-

" lytic reactions-'Hand i'or regenerating catalysts.

A further obiectisto combine he beggar reactantswith vthe production of`reaiztijv'ating s containing a controlled "amount oi' oxygen in i.auch. almeriense@ .live averetion oi' 4bo thstepslira,continuouscatalytic proef 'fromztne fonowing (detailed 'desonptionand ao,-

In generalfizmy'inventi ogtmplates. (k1) forfaffuel lnsuch of the airintroduced into thegcombustion zone,

ot-ille" which is subtreeworawhich contains' less stantially oxyg@oxygen .than lor catalyst regeneration, :(12) i:mixing withfthef'ho't`ihre-'gas sufllcient air or ..othergoxygene-containinggas to give aygas of the desired dwfoxyn content, (3). passing the lowoxygenaflystgi'orf a stream or-.roa'otanto sonofornaceVK indi t thisinvention, a d` .reforming process whip incluy es.

the catalyst wiii'be. df b'jd not his even to Gasoline to '4 .throughpipe-.I l heat exchanger I2 treated gasoline, furnace I6 where it berznfor` 2| the treated. gasolio pipo zz or pipe 2r, respectively;'topipo' 2 flow of gasoline through catalyst' chamhe sift- 2,0 and 2| iscontrolled by valves 25-and 21 in` ipes in pipes I9 and 23,respectively, Finally, the hot treated gasoline is passed from pipe 24.through heat exchanger il where itis cooled by Athefin'` cominggasoline,'and then flows by means'of. pipe 29 to-conventionalpurification steps such .as hy-` drogen sulilde removal, fractionation,etc. for the production of a blending stock or finished motor fuel.

simultaneously with `tnetdesuirunzonori and/or Otherr objects o! theinvention will be apparent assatai reforming of the gasoline in oneoithe two catalyst chambers, an oxygen-containing gas is passed throughthe other chamber, which oontai'ns deactivated catalyst. to burn oi!heavy 5.

carbonaceous material which has been deposited on the catalyst surfaceduring a preceding conversion cycle. The manner of producing the ria-` ygenerating gas will now be described.

:The furnace I8 is heated by the burning oi' any kind of i'uel.k Inorder to simplify the ex-v j planation of the invention, the operationof the furnace will be described referring to a high 4 methane contentgas which is available in large quantities at refineries, and which is apreferred fuel. However, free-hydrogen-containing gases,

` fuel oil, coke, etc., could be used if desired by means of obviousmodiilcations. The fuel, in this case gaseous, is fed through pipe 30into furnace I6. Air impelled by blower 32, or any suitable .equivalentthereof, flows through pipe 33 and is fed into furnace I6 through oradjacent to pipe 30 to supply the oxygen necessary for supportingcombustion of the fuel. vThe furnace I6 ordinarily is operated under apressure of about 5 to 15 pounds per square inch gauge, and the relativevolumes ot fuel and air are regulated so as to use up almost all of theoxygen, Thus the oxygen content of the combustion gases leavingA furnaceI6 may o generally be from zero to about one per cent. jConditions aremaintained so that said oxygen v @nicht e 65 I8 and 22 respectively,andby valves 2611.111

is always lower than thatdesired in the -tion gases.- The products ofcombustion ce Il through pipe. 34, and may then `to pipe Il, or-to pipe38, or to both, on may be vented through pipe I8.

ess combustion gas which is not required for. neration, but which may beused to help y Alieni/incoming gasolinein vheat exchanger I2, is

lbypassed around the catalyst chambers by means r per. A small stream ofair from pipe 33 is passed around furnace I0 by means of pipe `r*15,vjoins theproducts of combustion in pipe Y31. The oxygen content of' thegas in pipe 31 is vcontrolled by valve 36,v which allows the desired'quantity of air to pass through so as to give a lowpercentage ofoxygen, usually in the range of about 0.5 to 3.0 volume per cent duringthe y' vinitial portion of the burning-of!v period. This hot flue-gas inpipe 31 thus admixed with a small percentage of oxygen flows either`through pipe I9 containing valve 4I into catalyst chamber 20, or throughpipe 40 containing valve 42 into cata.-

lyst chamber 2i. In'the catalyst chamber, the carbon and heavy residuedeposited on the catalyst during the previous gasoline processing cycleare burned off gradually and the catalyst is thus regenerated. Theregenerating gas, now somewhat increased in temperature, passes intopipe 128' from catalyst chamber 2n or 2| through pipe I2 containingvalve I5 or through pipe 44 containing valve I6, respectively. Thus, thestream of spent" regenerating gas is mingledy with the y portion oi' thegaseous products of. combustion vifl'xichl was by-passed around thecatalyst chambers in pipe 38, and the hot gases then leave the system byway of vent 41, passing rstthrough heat exchanger I2 to heat thegasoline which is just entering the system. j

It will be understood, of course, that when catalyst lchamber 20, forinstance, is on stream for .catalytic treatment of the gasoline, valves25 and 2l are open, allowing heated gasoline to pass over thel catalyst,while the valves 26 and 28 are closed. Meanwhile valves 4I and 45 areclosed,

and valves 42 and may be open, thusallowing regenerating gases to passthrough catalyst chamber su. l and purging as described below, o! thecatalyst This continues until regeneration.

in chamber Il is completed". Then valves 4I and 4l are closed, and allthe products of combustion may be by-passed through pipe Il. yBefore andafter the passage of oxygen-containing'gas over the catalyst for burningo!! carbon, the valve I6 is closed and hot, substantially engen-treeproducts oi' combustion are passed from pipe I1 throughrthe catalystchamber in order to purge it of, first, residual gasoline, and second.residual oxygen-containing regenerating gas.' When the catalyst inchamber 2li becomesdeactivatcd tosuch an extent that the reactions areslowed to an uneconomic rate,'valves 26 and .28 are opened, and valves25 and 21 are closed, thus causing the gasoline to pass over theregenerated catalyst in chamber 2|. Purging and regeneration of thecatalyst in chamber 20 is then started by opening va1v`es 4I and 45. Inthis manner, the catalytic conversion is always being carried out inonel chamber, while the catalystv in the other chamber is being purged,regenerated, or is standing by after regeneration. Of course, thepurging and regeneration may be regulated so as to require the samelength of'time as the conversion cycle. For periods during which thesystem is being put onstream,'or during which one catalyst chamber isbeing used for gasoline processing while regeneration of the other hasbeen completed, or at other times in which not all the products ofcombustion are needed for heating purposes in heat exchanger I2, theexcess iiue-gasmay pass from the system through vent 48. Furthermore,vent 48 is usedto vary `the vol; ume of gaspassing vto lines 3l and 38,especially when the oxygen content of the gas in line 311s' beingincreased or reduced by means of valve 38,! as will be described laterin more detail.

Occasionally, it may be found de able,'if the catalyst used will permit,to introduce water or steam from line 5i either directly into iumace I8via line 52 or into the combustionproducts in line 34 via line 53. Thissteam may be uti' lized tor assist in controlling the temperature of thecombustion products and thus add to the yilexibility of operationattainable by' use or my invention. v

Additional controll of temperatures is accomplished by means ofby-passes around the var- 'back-pressure regulators the compressoren'blower discharge line II to the iinal venting "and 4I may be regulatedwithin the indicated pressure range by suitable not shown in the draw-Thc design o! theiurnace may be varied according .to the volume ofreactantsto be heated, the temperatures required for reaction "andreactivation, the volume of reactivating gas desired, the fuel used.'the possible corrosive effects of reactants and vfuel. etc. TheAgasoline nows. y through tubes in the furnace which are arranged ,f soas` to pick up radiant heatfjrromthe combustion. In'this way, thegasoline may leave the tolerate high concentrationsv of steam, a fuel`Vfurnaceheated to the'proper reaction tempera.-v ture ywhile theVcombustion gases are cooled by.v

loss of heat 1 to the incoming gasoline untiltheir temperature issuch-.that after admixture-with the cold by-passcd air, thelow-oxygen-content gas thus produced is at" the proper temperature. l

for carrying out regeneration. No separate cooling means is required inthe regenerating gas line between the furnace and the catalyst chamber.If desired, some steam from line 5i may be used asanadjunct to ciectfinal control of temperature.

Any fuel may be utilized 'inl'carrying out invention; however, `somediscrimination in thechoice of fuel may be necessary in certain cases;

For instance, if a catalyst is used which cannot which contains a highpercentage of free or combined hydrogen would not be suitable, and/elbetterl choice would be coke or fuel oil. i The desired temperature ofthe' reactivating gas will depend upon the catalyst and sometimes uponthe stage of regeneration. That is, it may be desirable to increase thetemperature somewhat. during the latter portionof a reactivation cycle.This may be accomplshedby increasing the oxygen content.

The basic control of the process is reduced to v the proportioning ofthe volumes of the fuel and air which are' mixed in the furnace, ofcombustion gasespassed to the catalyst chamber, and of the air which isby-passed for controlling the oxygen content 4oi! the regenerating gasstream.

. In its simplest aspects,'the control comprises regious heatexchangers,asiillustrated by pipe 48 controlled by valve 50, which allows anydesired amount of the gasoline stream to pass around heat exchanger I4.Ot course, recycling a portion of the treated gasoline stream orfractionsv thereof, or light gases, and other variations of a catalyticprocess of this type maybe resorted to. However, such modications do notform a-part of this invention, and are therefore not'discussed indetail. Obviously, more than two catalyst chambers may be used in theprocess in accordance with well known principles oi catalyticoperations. l

Combustion of fuel vin furnace -|6 is carried out at moderatesuper-atmospheric pressures oi' 5 to 15 pounds per square inch gauge, orsometimes up to 50 pounds per square inch gauge,V

which pressures are sufficient to give proper combastion, and tomaintain now oi the combustion atmosphere on through the catalystchambers and heat exchangers without further compression. This is veryydesirable, in that it 'eliminates the necessitytor compression of hotgases.

The system pressure from the viuel line 30 and 75 ulation of thevalvcsor flow controllers in the lines, 33, 3l, and 35 to produce a gaslmixture of any desired oxygen concentration up to a fairly largeproportion ot air. This covers all ordinary reactivationsteps, andindicates the flexibility and simplicity of operation of my process.

Operating controls such as proportioning now controllers actuated by thetemperature of the eiliuent gas from the catalyst bed may be ern-Aployed if desired. The preferred method of op-` erating comprisespassing a constant volume of regenerating gas overthe catalyst andvarying the voxygen content by increasing or decreasing the flow throughlines 35 and 48, to' give a greater or smaller percentage of oxygen4while mainteniing constant volume. Thus, toward the endo! a`reactivation period, the ,volumeof gas vented throughv `line '4 8 .maybe increased, .while valvey 36 is opened a little more tosupply `agreater volpurging, the 'vent'valves may also be closed suiciently toprevent a change in the volume of purge gasfc When conversionv in acatalyst chamber has. fallen to an undesirably slow rate or-when too Imuch side reaction is occurring, or in other words f when for anyreason'i't'is desired to initiate re- When valve 36 is closed to permitvgeneration of a catalyst mass, the flow of reactants over the particularvolume o! catalyst is stopped and hot regenerating gases are caused topass through the chamber. Initially, the reactants must b`e purged fromthe reaction vesselA and, in the case of hydrocarbons it is necessary todo this with an oxygen-free gas. In my process, this oxygen-free gas may'come from furnace I6 through lines 3l and 31, valve 36 being closed asdescribed above. A quantity of steam from line may sometimesadvantageously be admixed with this gas to lower any residual oxygencontent and to aid in the purging of hydrocarbons. Or steam alone or anyother suitable inert gas or mixture of inert gases may be utilized ifthe type of catalyst will permit.

After the catalyst bed is purged substantially free of volatilehydrocarbons, combustion is from values at the blower dischargejustsuflicient y to overcome the total pressure drop in the system to highervalues of 50 pounds gauge or more maintained by pressure regulators onthe effluent gas lines. In someY cases, higher pressures are beneficialini shortening the iinal stages of reactivation. However, the preferredpressure range for most processes is from about 5 to about 15 pounds persquare inch gauge.

According to present knowledge the reactivating combustion may bedivided into two phases according to the potential'rate of combustion.The rst or rapid phase includes the period required for removal of thesurface coating of carbonaceous material from the catalyst granules. Inthis period the oxygen content ofthe cornbustion must be very low,generally of the order of from less than l to about 3 volume per cent toprevent excessive temperatures at the combustion front or zone ofintense oxidation.

The combustion front'proceeds uniformly in the direction of reactivatinggas ilow and eventually reaches the end of the catalyst bed. Thisterminates the first phase of reactivation. 'I'he second phase includesthe combustion of cai'- bonaceous material mostlybeneath the surface ofthe catalyst granules, and higher oxygen concentrations in thecombustion atmosphere are frequently permissible and necessary torapidly complete the reactivation. In this phase the Weight ofcarbonaceous material removed is relatively small compared to the totalweight originally present, and the rate of combustion is much slower.Oxygen concentration of the order of 2 to 10 per cent or more may beemployed without producing excessive temperatures.v i

At the completio-n of the reactivating combustion, the iiow ofoxygen-containing gas is discontinued, and the catalyst is again purgedwith substantially oxygen-free gas to prepare said catalyst for furtherconversion service.

As heretofore pointed out, the adjustment of my process to any existingor desired set of consulfurization process, and is erence to thedrawing.

ditions involves only proper control ot the volume andxemperature of theindicated gas streams being mixed at a single point in the system.

The following example will serve to illustrate the speciiicoperatinfdeinsils of a gasoline dedescribed with rei'- I ExampleSulfur-bearing barrels per day (16,160 pounds per hour) and at normalatmospheric temperatures is .forced by pump i0 through heat exchangerI2.. which gives up 1,134,000 B. t. u. per hour to the gasoline. Passageof the thus-warmed gasoline through heat exchanger I4 increases its heatcontent by 4,300,000 B. t. u. per hour. Then 3,500,000B. t. u.

per hour is added to the gasoline in furnace I6 to increase itstemperature to '765 F.

The heated gasoline then passes through one of the catalyst chamberscontaining'bauxite. wherein a high percentage .of the sulfur compoundspresent in the gasoline is converted to hydrogen sulfide. On theaverage, 32.4 pounds of carbon per hour is deposited on the catalyst.The eilluent gasoline is at a temperature of 750 F., and after passingthrough heat exchanger 14,. leaves the system at a temperature in theneigh` borhood of 325 F. Further treatment is required for hydrogensulilde removal and stabilizationof the desulfurized gasoline.

The heat in furnace I6 comes from the combustion of 76 cubic feet perminute (measured at normal temperature and pressure) of dry natural gaswith 760 cubic feet per minute of air. This quantity 'of air issufficient for the complete combustion of. the fuel, and a substantiallyoxygen-free nue-gas is thus produced. Air by-pa'ssed through pipe 35 andvalve 36 is introduced to give a controlled low oxygen content gas inline 31. During most of the regeneration, the oxygen v content is heldto below 3 per cent. For the sake of simplicity, the conditions at onestage of the process will be described, namely, when the regeneratinggas contains 1.9 per cent oxygen, due to the addition of 84 cubic feetper minute of cold by-passed air. The volume of regenerating gas is 920cubic feet per minute and it is passed at an initial temperature of '700F. through a chamber which contains deactivated catalyst.

Combustion of carbonaceous material occurring in the chamber causes thetemperature of the regenerating gas to increase to 1075 F. This hot,spent regenerating gas passes through heat exchanger I2 .for heating theincoming gasoline and then leaves the system. Each catalyst charnber isutilized in the cycles of desulfurization, purging, regeneration, andpurging as heretofore fully explained.

The advantages of my invention lare many. Most important are theeconomies of equipment and operating costs which are made possible. Forinstance, in a process such as that described in detail above, initialinvestment costs for apparatus for heating reactants and for producingand handling regeneration gas are lower by 15 to 30 per cent than thosefor a conventional plant. Great savings in operating costs are obtainedthrough the use of only one portion of fuel both to heat the reactantsand to form a regenerating gas. By this means, a reduction of at leastr50 per cent in the quantity of fuel required for operation is realized.`r`The heat exchange ar-l rangements insure thatl onlyV a minimumquantity of heat is 10st from thesystem. Also,powe'r costs gasoline in aquantity of 1,500l

By utilizing my invention, a very desirable flexibility of operation isattainable, whereby the oxygen content and temperature of theregenerating gas are easily controlled to give proper regenerationconditions at all times.v

As heretofore pointed out,.-this invention.A is ini, no way limited tothe specific example described,

but may be used with advantage in ajgreat nurn-y 2,338,581 I for"vblowing air, etc.. are lowered, and the regenerating gas is furnished ata satisfactory pressure without the necessity of compressingv a hot gas.

4naceous matter is gradually deposited on said j',

content of' lsaid hydrocarbons,` whereby carbof catalyst lowering theactivity-thereof, admixing ber of catalytic processes. Thus,jmyinvention is not limited to the reactivation of' any particular type ofcatalyst nor to anyspeciiic 'conversion-in.

which catalysts are deactivated bythe deposition of carbonaceousdeposits. In general, the cata-QV lysts to be reactivated according-tothe' terxnsof' ff" the foregoing disclosure are those which are -re` L.

stored to a suitable activity under-the speciiied controlled conditionsbut which are susceptible to deterioration if the saidA specitledconditions are exceeded during reactivationtreatmentr. Examples of suchmaterials are vthe various contact catalysts classified as clay-type andmineral'orevv materials and natural or synthetic metal oxides includingthe difiicultly reducibie oxides alone .or

in mixtures with each other and/or promotedwith other metals or metalsalts. i Specific examples are bauxite and bauxite impregnated Withchromium, zirconium, and other oxides used in cracking. dehydrogenation,aromatization and deair with the hot; substantially oxygenffree iluegasin controlled amounts te give a regenerating Y gasf'oi Iowroxygencontent, contacting said Avlowf. g

CXYgehcontent gas with the ldesulphurizaticn i-catalyst of lloweredactivity'for the: regeneration ofl said'catalyst.'l v and periodicallyalternating the i .generating gas over each' separatev catalyst mass`-so'` as tri/.maintain 'the activity of the catalyst. c

" 2 .1'A process for the catalytic -desuiphurizaf 1 tionf ofhydrocarbons 4wherein the catalyst' becomes deactivated by thedeposition of c'arbona- .ceousmaterials thereon which comprises passing1sulphur-bearing."hydrocarbons in indirect heat sulfurizationconversions and composite catalysts,A

prepared from silicon and aluminum oxides and activated silicates.- vyThe terms reactivation used herein assynonyms; I claim: l. Aiprocess forthe catalytic desulphurization and regeneration are vof hydrocarbonswherein the catalyst becomes deactivated by the deposition ofcarbonaceous materials thereon which comprises passing sulphur-bearinghydrocarbons in indirect heat exchange with hot spent regenerationgases, passing the so-heated hydrocarbons in indirect heat exchange withhot desulphurized hydrocarbons, bringing the total reactant stream oisaid sulphur-bearing hydrocarbons up to reaction temperature in a.heating means, burning fuel in said heating means in the presence of anamount of air such that a ilue gas containing less than about one percent of.oxygen is formed by combustion, purging residual reactants froma deactivated exchange with hot spent regeneration gases, passing theso-heated hydrocarbons in indirect ,heat exchange with hot desulphurizedhydrocarbons,`

bringing the total reactant stream of said sulphur-bearing hydrocarbonsup to reaction temperaturein a heating means, burning fuel in saidheating means inthe presence of an amount of air such that av iiue gascontaining less than about 'l' one per cent of oxygen is formed bycombustion, purging residual reactants from a deactivated catalyst bymeans of said gas, thus heating the sulphur-bearing hydrocarbons whileproducing a' hot substantiallyoxygen-free ilue-gas, contact-- ing theheated hydrocarbons with an active desulphurization catalyst forreducing the 'sulphur content of said hydrocarbons, whereby carbonaceousmatter is gradually deposited onl s aid'cataA lyst lowering the activitythereof, admixing air with the hot substantially oxygen-free :due-gas incontrolled amounts to give an initial 'temperature f of approximately'100 F. and a ilnal temperature of approximately 1075 F. in thedeactivated cata. lyst bed, contacting said low-oxygen-content gasl withthe desulphurization catalyst of lowered activity for the regenerationof said catalyst. and

-periodically alternating the flow of sulphur-bearing hydrocarbons andregenerating gas over each separate catalyst mass so as to maintain thelactivity of the catalyst.

' JESSE A. GU'YER.

5j catalyst by means oi' said gas, thus heating the f" sulphur-bearinghydrocarbons while producing a 'hot substantially oxygen-free iiuey gas,c ontacting the'heatedl hydrocarbons with an active de` jsulphurlzation, catalystv lor; reducing the sulphur 1

